JP2010124543A - Polymer actuator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer actuator that is driven by a low voltage even in a state without the presence of water and is favorable in driving response. <P>SOLUTION: The polymer actuator 10 is so configured that electrode layers are in contact with each other with nonaqueous polymeric solid electrolyte containing ionic liquid and a macromolecular component in between. When power is supplied from an external power supply 15, the electrode layers absorb or desorb ions supplied from the ion liquid to charge or discharge the actuator and the actuator is thereby driven. In this polymer actuator, a power collecting body having a higher electrical conductivity than the electrode layers and formed by adhesively bonding metal power with binder resin covers at least part of the electrode layers and connects to the external power supply. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer actuator having a polymer solid electrolyte sandwiched between electrodes and improved responsiveness.

  In recent years, in the fields of medical equipment and micromachines, there is an increasing need for transducers such as small and lightweight actuators and sensors. In addition, in the fields of industrial and personal robots, there is an increasing need for transducers that are light and flexible.

  From this point of view, polymer actuators are attracting attention as actuators that are lightweight and have a flexible drive section. Various types of polymer actuators have been proposed so far. For example, it comprises a polymer actuator (see Patent Document 1) that utilizes a change in the shape of a hydrous polymer gel caused by a stimulus such as temperature change, pH change, and electric field application, an ion-exchange resin film, and electrodes joined to both surfaces thereof. There has been proposed a polymer actuator (see Patent Document 2) that causes a curve and deformation by applying a potential difference between electrodes on both surfaces in a water-containing state of an exchange resin film. Especially in the latter, bending and deformation instantly appear in response to the polymer actuator after application of the electrode and show very excellent responsiveness, but on the other hand, its application range is limited because it operates only in a water-containing state. There is a problem of being done.

  As a means for overcoming these problems, a polymer actuator comprising a soft polymer dielectric and a flexible electrode has been reported (see Patent Document 3). This type of polymer actuator does not require water for operation, and the operation of the actuator is not a mass transfer phenomenon such as ions, but is due to an electron transfer phenomenon which is a faster process, so it is very responsive. It is excellent. However, on the other hand, a very high voltage of about several thousand volts is required for the operation, and there is a problem that the application range is limited from the viewpoint of safety.

  In order to overcome this problem, a polymer actuator in which an electrode made of an ionic liquid, a fluorine-based polymer, and a single-walled carbon nanotube is bonded to both surfaces of a non-aqueous polymer solid electrolyte made of an ionic liquid and a fluorine-based polymer (non- Patent Document 1) and a polymer actuator (Patent Document 4) in which electrodes containing activated carbon are bonded to both surfaces of a nonaqueous polymer solid electrolyte made of an ionic liquid and a block copolymer have been reported. These polymer actuators are driven at a low voltage of about several volts even in the absence of water, but have a problem that the response is poor due to the high resistance of the electrode layer.

  Therefore, a configuration in which a metal thin film is provided in contact with two electrodes of a polymer actuator has been reported. As a method for providing a metal thin film, for example, a method by vacuum vapor deposition or sputtering, a method of bonding a metal foil (see Non-Patent Document 2), and the like have been proposed. However, the former requires a vacuum process, which makes it difficult to provide a polymer actuator at a low cost due to complicated manufacturing equipment, and when the polymer actuator is made of a fluororesin, There is a problem that the adhesion force of the molecular actuator is weak, and the metal thin film formed easily falls off.

  Also, the method of laminating a metal foil has a problem in handling and durability, such as the adhesion between the metal foil and the polymer actuator is not good and is easily peeled off, and it is easily broken because it is thin. When a high strength metal foil is used to overcome this problem, even if the resistance is improved, the operation of the actuator is hindered, so it cannot be said that it is useful for improving the performance of the polymer actuator.

JP-A 63-309252 Japanese Patent Publication No. 7-4075 Special table 2003-505865 gazette PCT International Publication No. WO2008 / 044546 Future Materials, Vol. 5, 10, p. 14, 2005 Sensors and Actuator A, 126, 173, 2006

  An object of the present invention is to solve the above-mentioned problems, and is a polymer actuator that can be driven at a low voltage in the absence of water and has good drive response. Is to provide.

  As a result of intensive studies, the present inventors have found that a current collector that satisfies specific requirements in a polymer actuator having at least two electrode layers and at least one non-aqueous polymer solid electrolyte layer sandwiched between the two electrode layers. It has been found that a polymer actuator in which the body layer is placed in contact with the electrode layer has good drive responsiveness and can be suitably used for various applications.

  The polymer actuator of the invention according to claim 1 of the present invention made under this knowledge has an electrode layer in contact with a nonaqueous polymer solid electrolyte layer containing an ionic liquid and a polymer component sandwiched from an external power source. A polymer actuator that is driven by power supply by absorbing and desorbing ions supplied from the ionic liquid and charging or discharging them. The polymer actuator has higher electrical conductivity than the electrode layer, and the metal powder is bound with a binder resin. The collected current collector layer covers at least a part of the electrode layer and is connected to the external power source.

Similarly, the polymer actuator of the invention according to claim 2 is the polymer actuator according to claim 1, wherein the collector layer has a maximum surface resistivity of 10 ⁻² Ω / □ and a tensile elastic modulus. It is 10 GPa or less.

  A polymer actuator according to a third aspect of the present invention is the polymer actuator according to the first or second aspect, wherein the metal powder is silver powder.

  A polymer actuator according to a fourth aspect of the present invention is the polymer actuator according to any one of the first to third aspects, wherein the binder resin is a urethane resin.

  A polymer actuator according to a fifth aspect of the present invention is the polymer actuator according to any one of the first to fourth aspects, wherein the current collector layer is formed by coating.

  A polymer actuator according to a sixth aspect of the present invention is the polymer actuator according to any one of the first to fifth aspects, wherein the non-aqueous polymer solid electrolyte is compatible with the ionic liquid and the ionic liquid. It contains at least one polymer block (P) and a block copolymer (R) having at least one polymer block (Q) that is incompatible with the ionic liquid. .

  A polymer actuator of an invention according to claim 7 is the polymer actuator according to any one of claims 1 to 6, wherein the electrode layer is selected from activated carbon, carbon black, carbon nanotube, and carbon fiber. It contains at least one carbon material.

  Since the polymer actuator of the present invention has a current collector layer having a low resistance, a potential difference is instantaneously applied between the two electrodes even at a location away from the connection from the power source, so that the drive response of the polymer actuator Good properties. In addition, the current collector of the present invention is flexible and can provide a polymer actuator excellent in drive performance and responsiveness without impeding the drive of the polymer actuator itself.

Preferred form for carrying out the invention

  The polymer actuator of the present invention has an electrode layer that is charged and / or discharged by adsorption / desorption of ions, and a non-aqueous polymer solid electrolyte sandwiched between the electrodes, and covers the electrode layer and a current collector layer have.

  The current collector reduces the resistance in the longitudinal direction of the polymer actuator. When driving a polymer actuator, a lead wire connected to the positive electrode / negative electrode of the power source is connected to the two electrodes constituting the polymer actuator, respectively, so that a voltage is applied between the two electrodes of the polymer actuator. Apply. At this time, when the resistance of the electrode constituting the polymer actuator is high as in the case of an electrode using the above-mentioned carbon material as an active material, a voltage is transmitted from the contact point between the lead wire and the electrode in the longitudinal direction of the polymer actuator. Since this requires time, the drive response of the polymer actuator is inferior. The current collector overcomes this.

  The current collector is used not only in a polymer actuator but also in an electrochemical device such as an electric double layer capacitor. In the case of an electric double layer capacitor, a metal layer such as aluminum foil or aluminum formed by plasma spraying is used.

The current collector layer of the polymer actuator of the present invention is configured by fixing metal powder with a binder resin. Also in the current collector of the polymer actuator, the resistance value is preferably low, and the surface specific resistance is 10 ⁻² Ω / □ or less, more preferably 10 ⁻³ Ω / □ or less.

  Unlike an electric double layer capacitor or the like, the current collector of the polymer actuator is required to be sufficiently soft and flexible so as not to hinder its driving. From these viewpoints, the tensile elastic modulus of the current collector layer is preferably 20 GPa or less, more preferably 10 GPa or less, and further preferably 5 GPa or less. In order for the current collector to function without breaking even when the polymer actuator is driven largely, the tensile break elongation of the current collector is preferably 0.05% or more, and more preferably 0.1% or more. And more preferred.

  The current collector constituting the polymer actuator of the present invention is not particularly limited as long as the above-mentioned conditions are satisfied. For example, metal powders such as gold, silver, copper, platinum, aluminum, and nickel, and, if desired, added Examples thereof include a film-like molded article made of carbon powder such as carbon powder, carbon nanotube, and carbon fiber, and a binder resin. These are preferable from the viewpoint of flexibility. From the viewpoint of conductivity, it is more preferable to be a film-shaped molded body composed of metal powder and a binder resin, and from the viewpoint of industrial economy, a film-shaped molded body composed of silver powder and a binder resin is particularly preferable. .

  Moreover, there is no restriction | limiting in particular as a component of binder resin contained in a collector, For example, resin etc. which are illustrated back as a binder of an electrode can be utilized. Among these, from the viewpoint of the flexibility of the current collector, polyester, (meth) acrylic resin, rubbers or their cross-linked bodies, or thermoplastic elastomers are preferable, and rubber from the viewpoint of long-term shape stability. More preferably, it is a crosslinked product.

  From the viewpoint described above, one particularly preferred example is a current collector containing silver powder and urethane rubber (thermosetting).

  In addition to the above, the current collector may contain an antioxidant, a UV absorber, a lubricant, a dispersant, a surfactant, a bulking agent, a reinforcing agent, a plasticizer, etc., as long as the scope of the present invention is not impaired. It may be contained in an amount of preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less with respect to 100 parts by weight of the electric body.

  Examples of the method of forming the current collector include a vacuum deposition method, an ion sputtering method, a thermal spraying method, and a method of applying and sintering nanometal particle-containing ink when the current collector is a metal thin film. . In the case where the current collector is a metal foil, a method of pressing the metal foil with heat or the like can be mentioned. When the current collector is composed of metal powder or carbon fine powder and a binder resin, a method of coating and curing (crosslinking) ink obtained by diluting these with a solvent or dispersing them in a solvent, separately formed into a film The method of crimping the collected current collector with heat or the like can be mentioned. Among these, in the present invention, since the adhesion between the electrode layer and the current collector layer is excellent, the metal powder and the binder resin and other components such as carbon fine powder that may be added if necessary are diluted with a solvent, A method is used in which paste, ink, and the like obtained by dispersion are directly applied to the electrode layer and bonded by curing.

  When the current collector is formed by coating, the coating method is appropriately determined depending on the viscoelastic properties of the ink obtained by dispersing metal powder, binder resin, and other components such as carbon fine powder that may be added if necessary. Examples thereof include spin coating, spray coating, die coating, bar coating, ink jet, screen printing, and gravure printing.

  There is no restriction | limiting in particular as an order which forms a collector layer, The method of forming a collector layer on the outer side of 2 types 3 layer structure of an electrode layer-non-aqueous polymer solid electrolyte layer-electrode layer, on an electrode layer A method of sandwiching a non-aqueous polymer solid electrolyte layer with a film of a two-type two-layer structure obtained by forming a current collector layer first, and pressure-bonding, current collector layer-electrode layer-non-aqueous polymer solid electrolyte layer 2 Method of laminating membranes of seed three-layer structure with non-aqueous polymer solid electrolyte surfaces facing each other, current collector layer-electrode layer-non-aqueous polymer solid electrolyte layer-electrode layer-current collector layer The method of forming can be mentioned.

  Examples of elements constituting the electrode include an active material having a large specific surface area, a binder resin for allowing the electrode to self-support in a film shape, and an ionic material as necessary. Active materials having a large specific surface area include, for example, carbon materials such as activated carbon, activated carbon cloth, carbon black, carbon nanotube, and carbon fiber, noble metal particles such as gold and platinum, titanium oxide, zinc oxide, and indium-tin composite oxide ( Examples thereof include metal oxide particles such as ITO. Among these, a carbon material is preferable from the viewpoint of industrial economy and electrochemical stability, and activated carbon, activated carbon cloth, carbon black, and carbon nanotube are more preferable from the viewpoint of the specific surface area.

  The binder resin constituting the electrode is not particularly limited, but a resin that is generally used according to the purpose can be used. For example, polyolefin resins such as polyethylene and polypropylene, polystyrene, poly α-methylstyrene, etc. Polystyrene resins, poly (methyl methacrylate), poly (ethyl methacrylate), poly (butyl methacrylate), poly (acrylic acid), poly (methyl acrylate), poly (ethyl acrylate), poly (butyl acrylate) and other (meth) acrylic resins, polyvinyl chloride , Polyvinylidene chloride, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene random copolymers, vinyl halide resins such as polytetrafluoroethylene, polytrifluoroethylene, polyethylene glycol terephthalate, polyethylene glycol naphthalene Polyester resins such as phthalate and polybutylene glycol terephthalate, polyamide resins such as nylon-6, nylon-6,6, nylon-9T, nylon-11, nylon-12, nylon-6.12. Thermosetting resins such as polycarbonate resins, unsaturated polyesters, epoxy resins, alkyd resins, phenol resins, thermosetting polyurethane resins, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber (styrene butadiene random copolymer) Polymers), rubbers such as acrylic rubber, nitrile rubber, norbornene rubber, silicone rubber, urethane rubber (including soft thermosetting polyurethane) or cross-linked products thereof, olefin-based thermoplastic elastomer (TPO), styrene-based thermoplastic Elastomer TPS), crosslinkable olefin thermoplastic elastomer (TPV), acrylic thermoplastic elastomer (eg, block copolymer of polymethyl methacrylate and polybutyl acrylate), polyurethane thermoplastic elastomer (TPU), polyester Examples thereof include thermoplastic elastomers such as thermoplastic elastomer (TPEE) and polyamide-based thermoplastic elastomer (TPAE). The above resin may be one in which the monomer unit constituting it is copolymerized with those exemplified as the monomer unit constituting another type of resin. Among these, polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, thermoplastic polyurethane resin, and thermoplastic polyurethane elastomer are preferable from the viewpoint of film forming property. In addition, since the electrode layer needs to be in close contact with a nonaqueous polymer solid electrolyte described later, it may be the same as or similar to the polymer constituting the nonaqueous polymer solid electrolyte exemplified later.

Although there is no restriction | limiting in particular as an ionic substance which comprises an electrode, A metal salt, organic onium salt, an ionic liquid etc. can be illustrated. Among these, from the viewpoint that the polymer actuator is required to operate in an environment without water, it is preferably an organic onium salt or an ionic liquid, and its ionic conductivity, and hence the operating speed of the actuator. From the viewpoint, an ionic liquid is more preferable.
As for the ionic liquid contained in the non-aqueous polymer solid electrolyte, the following general formulas (I) to (V) can be given as examples of organic cations.

(Ｉ）式中、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立に水素原子、または炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状または分岐状のアルケニル基、炭素数６〜１５のアリール基、炭素数８〜２０のアラルキル基、炭素数２〜３０のオリゴアルケニレンオキシド基から選ばれる基を表す。

In formula ^{(I), R 1, R 2, R} 3 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, C2-10 straight-chain or branched, A group selected from an alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 8 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms.

（II）式中、Ｒ^４は、水素原子、または炭素数１〜１０の直鎖状または分岐上アルキル基、炭素数２〜１０の直鎖状または分岐状のアルケニル基、炭素数６〜１５のアリール基、炭素数８〜２０のアラルキル基、炭素数２〜３０のオリゴアルケニレンオキシド基から選ばれる基、Ｒ’は炭素数１〜６の直鎖状または分岐状のアルキル基、ｎは０〜５の数を表す。

(II) In the formula, R ⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, or 6 to 15 carbon atoms. A group selected from an aryl group having 8 to 20 carbon atoms, an oligoalkenylene oxide group having 2 to 30 carbon atoms, R ′ is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 0 Represents a number of ~ 5.

(III）式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８はそれぞれ独立に水素原子、炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状または分岐状のアルケニル基、炭素数６〜１５のアリール基、炭素数８〜２０のアラルキル基、炭素数２〜３０のオリゴアルケニレンオキシド基から選ばれる基を表し、Ｒ^５〜Ｒ^８のうち、２つの基が共同して環構造を形成していてもよい。

(III) In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight chain having 2 to 10 carbon atoms or Represents a group selected from a branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 8 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and 2 of R ^{5 to} R ⁸ Two groups may jointly form a ring structure.

(IV）式中、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２はそれぞれ独立に水素原子、または炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状または分岐状のアルケニル基、炭素数６〜１５のアリール基、炭素数８〜２０のアラルキル基、炭素数２〜３０のオリゴアルケニレンオキシド基から選ばれる基を表し、Ｒ^９〜Ｒ^１２のうち、2つの基が共同して環構造を形成していてもよい。

(IV) In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a straight chain having 2 to 10 carbon atoms. Or a group selected from a branched alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 8 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and among R ^{9 to} R ¹² , Two groups may jointly form a ring structure.

（Ｖ)式中、Ｒ^１３、Ｒ^１４、Ｒ^１５はそれぞれ独立に水素原子、または炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状または分岐状のアルケニル基、炭素数６〜１５のアリール基、炭素数８〜２０のアラルキル基、炭素数２〜３０のオリゴアルケニレンオキシド基から選ばれる基を表し、Ｒ^１３〜Ｒ^１５のうち、２つの基が共同して環構造を形成していてもよい。

(V) In formula, R <^13> , R <^14> , R <^15> is respectively independently a hydrogen atom or a C1-C10 linear or branched alkyl group, C2-C10 linear or branched. Represents a group selected from an alkenyl group, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 8 to 20 carbon atoms, and an oligoalkenylene oxide group having 2 to 30 carbon atoms, and two groups among R ^{13 to} R ¹⁵ May jointly form a ring structure.

Among these, the imidazolium cation represented by the general formula (I) is preferable from the viewpoint of ion conductivity and availability of the ionic liquid. Among these, from the viewpoints of the melting point and viscosity of the ionic liquid, R ¹ and R ² in the general formula (I) are preferably straight-chain or branched alkyl groups having 1 to 6 carbon atoms ^, More preferably, R ² is a different group. As an example of the most preferable organic cation, an ethylmethylimidazolium cation (EMI ⁺ ) can be mentioned.

Examples of anions constituting a suitable ionic liquid used in the present invention include halogen-containing anions, mineral acid anions, organic acid anions, and the like. Specific examples of the halogen-containing anion or mineral acid anion include PF ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ N ^{_{-, (C 2 F 5 SO}} 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SO 4 2-, (CN) 2 N -, and NO ₃ ^- can be exemplified. Examples of the organic acid anion include RSO ₃ ⁻ and RCO ₂ ⁻ . R is an alkyl group, an allyl group, an alkenyl group, an aralkyl group, an aralkenyl group, an alkoxyalkyl group, an acyloxyalkyl group, a sulfoalkyl group, an aryl group, or an aromatic heterocyclic residue such as a benzene ring, a naphthalene ring, or an anthracene ring. There may be a plurality of cyclic structures or branched structures. Among these, PF ₆ ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , BF ₄ ⁻ , (CF ₃ SO ₂ ) ₂ from the viewpoint of ionic conductivity and availability of ionic liquids ^{_{N -, (C 2 F 5}} SO 2) 2 N -, (CN) 2 N - is preferable, _{(CF 3 SO 2) 2 N} -, (C 2 F 5 SO 2) 2 N - etc. sulfonylimide of System anions are preferred.

  From the above, examples of the ionic liquid suitably used in the present invention include an ionic liquid composed of a combination of the above-described organic cation and anion. These may be used alone or in combination. Examples of preferred ionic liquids include ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI), ethylmethylimidazolium bis (pentafluorosulfonyl) imide (EMIPFSI), butylmethylimidazolium bis (trifluoromethanesulfonyl) imide ( BMITFSI) and butylmethylimidazolium bis (pentafluorosulfonylimide) (BMIPFSI). Among these, EMITFSI and EMIPFSI are preferable from the viewpoint of ionic conductivity of the ionic liquid, and EMITFSI is a more preferable example from the viewpoint of availability.

Even when the electrode is not a polarizable electrode, for example, an electrode having a pseudo double layer capacity may be used. Examples of active materials that provide such an electrode include ruthenium oxide (RuO ₂ ), iridium oxide (IrO ₂ ), ruthenium-tin composite oxide (RuO ₂ -SnO ₂ ), and ruthenium-molybdenum composite oxide (Ru— VO), noble metal oxides such as ruthenium-vanadium complex oxide (Ru-VO), nickel oxide (NiO), tungsten oxide (WO ₃ ), cobalt oxide (Co ₃ O ₄ ), molybdenum oxide (MoO ₃ ), oxidation Examples thereof include metal oxides such as titanium (TiO ₂ ), conductive polymers such as polypyrrole, polyaniline, polythiophene, and polythiophene derivatives.

The non-aqueous solid polymer electrolyte used in the present invention is not particularly limited, but is at least 10 ⁻⁶ S / cm or more, preferably 10 ⁻⁵ S / cm or more, more preferably 10 in the absence of water. ^It is a non-aqueous polymer solid electrolyte having an ionic conductivity of ⁻⁴ S / cm or more. If the ion conductivity is lower than this, it is not preferable because the response of the polymer actuator is inferior.

  Examples of such non-aqueous solid polymer electrolytes include those composed of a polymer and an ionic liquid, and those composed of a polymer, an organic solvent and an ionic liquid. Among these, it is more preferable to use a polymer and an ionic liquid from the viewpoint of ionic conductivity and from the point that performance degradation due to volatilization of the organic solvent can be ignored.

  As a polymer constituting the non-aqueous polymer solid electrolyte, in addition to the polymer equivalent to the binder resin constituting the electrode layer described above, as a preferred example, a polymer block compatible with the ionic liquid (A) used ( Examples thereof include a block copolymer (R) having at least one polymer block (Q) having at least one P) and incompatible with the ionic liquid (A). Examples of the polymer block (P) are esters of (meth) acrylic acid and alkanols having 1 to 3 carbon atoms; (meth) acrylic acid and alkylene glycols having 2 to 4 carbon atoms, dialkylene having 4 to 6 carbon atoms Monoester of glycol or C6-C9 trialkylene glycol; ester of (meth) acrylic acid and C2-C4 alkoxyalkanol; (meth) acrylic acid and C4-C6 dialkylene glycol or At least one homopolymer block or copolymer selected from ester of monoalkylene or monoethyl ether of trialkylene glycol having 6 to 9 carbon atoms; and ester of (meth) acrylic acid and aminoalkanol having 2 to 4 carbon atoms. There may be mentioned polymer blocks.

  As the polymer block (Q), a polymer block having an aromatic vinyl compound unit as a repeating unit; a crystalline polyolefin block; a polymer block of a methacrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms; a polycyclohexyl methacrylate block A polyisobornyl methacrylate block; or a random copolymer block of n-butyl methacrylate or isobutyl methacrylate and isobornyl methacrylate.

  The block copolymer (R) may be a condensation polymerization type block copolymer. For example, when the block copolymer (R) is a thermoplastic polyurethane, the polymer block (P) may be a polyester polyol. , A polyether block, a polycarbonate polyol, a polymer block made of a polymer polyol such as a polyester polycarbonate polyol, and the polymer block (Q) is a bifunctional isocyanate such as 4,4′-diphenylmethane diisocyanate and 1,4-butane. Examples thereof include a polymer block composed of a reaction product with a chain extender such as diol.

As a particularly desirable example of the non-aqueous polymer solid electrolyte, for example, when ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI) is used as the ionic liquid (A), the polymer block (P) is poly Methyl acrylate, polymer block (Q) is polystyrene, block copolymer (R) is a block copolymer whose sequence is QPQ, ie polystyrene-b-polymethyl acrylate-b-polystyrene Alternatively, the polymer block (P) is a polyester block composed of adipic acid and 1,4-butanediol, and the polymer block (Q) is composed of 4,4′-diphenylmethane diisocyanate and 1,4-butanediol. A polymer block, and the sequence of the block copolymer (R) is (PQ) _n ; (n Is a multi-block copolymer polyurethane having a number of 1 or more.

  The polymer actuator of the present invention can operate in air, water, vacuum, and organic solvent. Moreover, you may seal suitably according to a use environment. There is no restriction | limiting in particular as an example of sealing material, Various resin etc. can be mentioned.

  EXAMPLES Hereinafter, although an Example, a comparative example, and a reference example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these. In addition, measuring instruments, measuring methods, and materials used in the following examples, comparative examples, and reference examples are shown.

(1) Ion conductivity measurement Equipment used: Chemical impedance 3532-80 manufactured by Hioki Electric Co., Ltd.
Assumed method: Measured using a complex impedance method, an AC four-terminal cell, and after conditioning the polymer solid electrolyte at 25 ° C./11 Rh% overnight or longer. Measurement temperature 25 ° C.

(2) DSC measurement A small amount of polymer or solid polymer electrolyte was taken and measured using a DSC-822e manufactured by Mettler. The temperature was raised from room temperature to a temperature equal to or higher than the glass transition temperature (Tg) at 30 ° C./min, and then held for 5 minutes to erase the heat history. Thereafter, the temperature was lowered to −100 ° C. at 10 ° C./min. After holding at −100 ° C. for 5 minutes, the process of raising the temperature to 200 ° C. at 10 ° C./min was observed.

(3) Tensile test equipment: Shimadzu Autograph AG-2000
The produced current collector film was subjected to a tensile test, and the tensile modulus was measured.

(4) Surface resistivity measurement device used: Electrical resistance measuring device ("Laresta-GP MCP-T610" manufactured by Mitsubishi Chemical Corporation)
The surface resistance was measured at five locations on the film-like test piece, and the average value was calculated.

(5) Actuator operation test As shown in FIG. 3, with respect to the polymer actuator 10 cut into a size of 15 mm × 5 mm, 10 mm is sandwiched between the copper terminal 12 and the copper metal terminal 13 in the length direction, and the actuator operates as an actuator. 5 mm was taken out into the air and used as a measurement cell. A potential control terminal and a current control terminal of a potentiostat 15 (HAB-151 manufactured by Hokuto Denko) were connected to the copper terminals 12 and 13. The copper terminal 12 is a working electrode, and the copper terminal 13 is a counter electrode, that is, a reference electrode. A target of a laser displacement meter (“LC-2440” manufactured by Keyence Corporation) 10 was determined at a position P of 4 mm from the tip of the portion of the polymer actuator 10 exposed to the air. In this state, the cell was fixed, a voltage of 1 V was applied from the potentiostat 15 between both electrodes of the polymer actuator 10, and the displacement amount was measured with the laser displacement meter 10. The displacement amount after 1 second of voltage application was D1, the displacement amount after 30 seconds was D30, and the value of D1 / D30 was used as an index of responsiveness. The closer this value is to 1, the better the response, and the closer to zero, the worse.

The materials used are shown below.
(1) Polystyrene-b-polymethylacrylate-b-polystyrene; It was synthesized by a living radical polymerization method using a copper (I) complex as a catalyst. Number average molecular weight (Mn) 186,400, molecular weight distribution (Mw / Mn) 1.73, polymethyl acrylate content in block copolymer 27% by weight, hereinafter sometimes referred to as SMS block copolymer .

  (2) Multi-block copolymer type thermoplastic polyurethane; “Kuramylon U2795” manufactured by Kuraray (a polymer block derived from a polyester polyol composed of 1,4-butanediol and adipic acid, 4,4′-diphenylmethane diisocyanate and 1, A multi-block copolymer type thermoplastic polyurethane composed of a polymer block composed of 4-butanediol was used as it was.

  (3) Ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI); purchased from Nippon Synthetic Chemical Co., Ltd. and used as it is.

  (4) Poly (vinylidene fluoride-ran-hexafluoropropylene) (P (VDF / HFP)); “Kyner 2801” manufactured by Arkema was purchased and used as it was.

  (5) Activated carbon: “YP-50F” manufactured by Kuraray Chemical Co., Ltd. was purchased and used as it was.

  (6) Acetylene black; “Denka Black” manufactured by Denki Kagaku Co., Ltd. was purchased and used as it was.

  (7) Silver paste A; “Bunny Height M-15” (silver paste containing silver particles and thermosetting urethane rubber) manufactured by Nippon Graphite Co., Ltd. was purchased and used as it was.

  (8) Silver paste B; “Dotite XA9015” (silver paste containing silver particles and polyester) manufactured by Fujikura Kasei Co., Ltd. was purchased and used as it was.

  (9) Silver paste C: “Dotite FA353N” (silver paste containing silver particles and polyester) manufactured by Fujikura Kasei Co., Ltd. was purchased and used as it was.

  (10) Aluminum foil: “My foil” (thickness: 12 μm) manufactured by Sumi Light Aluminum Foil Co., Ltd. was purchased and used as it was.

  Other purchased reagents and materials were used as they were.

Reference Example 1 Production of Polymer Solid Electrolyte Membrane (1) 1 g of SMS block copolymer and 1.61 g of EMITFSI are dissolved in tetrahydrofuran and cast on a smooth substrate to give a polymer solid electrolyte having a thickness of 100 μm. Membrane A was obtained. The obtained solid polymer electrolyte membrane A had an ionic conductivity of 1.42 × 10 ⁻³ S / cm.

  (2) When the DSC measurement of the SMS block copolymer and the polymer solid electrolyte membrane A obtained in (1) was performed, it was found that EMITFSI was unevenly distributed in the polymethyl acrylate block. Therefore, in this case, the polymethyl acrylate block corresponds to the polymer block (P), and the polystyrene block corresponds to the polymer block (Q).

Reference Example 2 Production of Polymer Solid Electrolyte B (1) 1 g of multi-block copolymer polyurethane and 2.5 g of EMITFSI were dissolved in tetrahydrofuran and cast on a smooth substrate to form a polymer solid having a thickness of 100 μm. An electrolyte membrane B was obtained. The obtained solid polymer electrolyte B had an ionic conductivity of 3.53 × 10 ⁻³ S / cm.

  (2) When DSC measurement was performed on the multiblock copolymer polyurethane and the polymer solid electrolyte B obtained in (1), EMITFSI was derived from a polymer polyol composed of adipic acid and 1,4-butanediol. It was found that it was unevenly distributed in the polymer block. Therefore, in this case, a polymer block derived from a polymer polyol composed of adipic acid and 1,4-butanediol is converted into a polymer block (P), and 4,4′-diphenylmethane diisocyanate, 1,4-butanediol and The polymer block consisting of corresponds to the polymer block (Q).

Reference Example 3 Production of Electrode Layer (1) Take 0.1 g of activated carbon, 0.06 g of acetylene black, 0.04 g of P (VDF / HFP) and 0.3 g of EMITFSI in a mortar and grind well with a pestle. Material was used.

  (2) The obtained bulk electrode material was sandwiched between PET films and hot pressed at 130 ° C. to obtain an electrode layer having a thickness of 100 μm.

Reference Example 4 Production of polymer actuator A
(1) The polymer solid electrolyte membrane A obtained in Reference Example 1 or the polymer solid electrolyte membrane B obtained in Reference Example 2 is sandwiched between two electrode membranes obtained in Reference Example 3, and the thickness is 300 μm. The polymer actuator which consists of a laminated structure of an electrode-polymer solid electrolyte-electrode was manufactured by performing a heat press using this press die.

  (2) Next, if necessary, a silver paste was applied to one side of the laminated structure obtained in (1) using a doctor blade (clearance 100 μm). This was dried and cured on a hot plate at 100 ° C. for 3 hours.

  (3) This operation was also performed on the other surface, and further vacuum-dried at 100 ° C. for 24 hours to produce a polymer actuator having current collector layers on both surfaces.

Reference Example 5 Production of polymer actuator B
A polymer in which the laminated structure obtained in Reference Example 4 is sandwiched between two aluminum foils and subjected to hot pressing using a 300 μm-thick press die so that the aluminum foil is thermocompression bonded to both sides of the laminated structure. An actuator was manufactured.

Reference Example 6 Preparation of Current Collector Film (1) A silver paste was applied to a PET film using a doctor blade (clearance 750 μm), and this was dried and cured on a hot plate at 100 ° C. for 3 hours. Further, it was vacuum dried at 100 ° C. for 24 hours. Only the PET film was peeled from here to obtain a current collector film. A tensile test was performed on this film to evaluate the tensile properties of the current collector film.

<< Examples 1 to 6 >>
Table 1 shows the data and measurement results for the polymer actuators of Examples 1 to 6.

<< Comparative Examples 1-4 >>
Table 2 shows data and measurement results for the polymer actuators of Comparative Examples 1 to 4.

  From the comparison between Examples 1 to 3 and Comparative Example 1 and Examples 4 to 6 and Comparative Example 2, the response of the polymer actuator may be improved by using a current collector layer having a small surface resistivity. Recognize.

  In Comparative Examples 3 and 4, the responsiveness of the polymer actuator is improved with respect to Comparative Example 1 and Comparative Example 2 by using aluminum foil as the current collector layer having a small surface specific resistance. However, in comparison with Examples 1 to 3 and Comparative Example 3 and Examples 4 to 6 and Comparative Example 4, when a current collector layer having a large tensile elastic modulus is used, the displacement amount of the polymer actuator is reduced. As a result, the performance is degraded, which is not preferable.

  The polymer actuator of the present invention has improved responsiveness without impairing the characteristics unique to the polymer actuator such as the magnitude of displacement, and is suitably used in the fields of medical equipment, micromachines, industrial robots, personal robots, and the like. be able to.

It is the schematic of the apparatus used in the operation | movement test of the actuator to which this invention is applied.

Explanation of symbols

  10 is an actuator, 12 and 13 are copper terminals, 15 is a potentiostat, and 18 is a laser displacement meter.

Claims (7)

The electrode layer in contact with the non-aqueous polymer solid electrolyte layer containing the ionic liquid and the polymer component is charged or discharged by adsorbing and desorbing ions supplied from the ionic liquid by supplying power from an external power source. In the polymer actuator to be driven, a current collector layer having higher electrical conductivity than the electrode layer and having a metal powder bound by a binder resin covers at least a part of the electrode layer, and the external power source A polymer actuator characterized by being connected to 2. The polymer actuator according to claim 1, wherein the current collector layer has a maximum surface resistivity of 10 ⁻² Ω / □ and a tensile modulus of 10 GPa or less. The polymer actuator according to claim 1 or 2, wherein the metal powder is silver powder. The polymer actuator according to any one of claims 1 to 3, wherein the binder resin is a urethane resin. The polymer actuator according to any one of claims 1 to 4, wherein the current collector layer is formed by coating. The non-aqueous solid polymer electrolyte includes an ionic liquid and one or more polymer blocks (P) that are compatible with the ionic liquid, and one or more polymer blocks (Q) that are incompatible with the ionic liquid. The polymer actuator according to claim 1, further comprising a block copolymer (R) having the polymer. The polymer actuator according to any one of claims 1 to 6, wherein the electrode layer includes at least one carbon material selected from activated carbon, carbon black, carbon nanotube, and carbon fiber.

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